Color photographic light-sensitive materials for color prints showingexcellent color reproduction

ABSTRACT

A MULTIPLE LAYER TYPE COLOR PHOTOGRAPHIC SILVER HALIDE LIGHT-SENSITIVE MATERIAL FOR COLOR PRINTS HAVING AT LEAST A BLUE-SENSITIVE PHOTOGRAPHIC EMULSION LAYER IN WHICH THE SPECTRAL SENSITIVITY OF THE BLUE-SENSITIVE SILVER HALIDE EMULSION LAYER IS LIMITED TO THE REGION OF ABOUT 440 TO ABOUT 460 NM., IN WHICH AT LEAST ONE DYE HAVING ITS ABSORPTION MAXIMUM AT A WAVELENGTH REGION SHORTER THAN ABOUT 440 NM. AND/OR IN A REGION OF ABOUT 460 TO ABOUT 520 NM. IS INCORPORATED IN THE BLUE-SENSITIVE PHOTOGRAPHIC EMULSION LAYER OF THE LIGHT-SENSITIVE MATERIAL AND/OR IN A LAYER COATED ON THE BLUE-SENSITIVE PHOTOGRAPHIC EMULSION LAYER.

United States Patent 01 ifice 3,746,539 Patented July 17, 1973 3,746,539COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS FOR COLOR PRINTS SHOWINGEXCELLENT COLOR REPRODUCTION Hideki Ohmatsu and Hirozo Ueda,Minami-ashigara,

Japan, assignors to Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa,Japan No Drawing. Filed Feb. 9, 1972, Ser. No. 224,933 Claims priority,appligation Japan, Feb. 9, 1971,

4 Int. Cl. G03c 1/14, 1/16, 1/18 U.S. CI. 96-68 13 Claims ABSTRACT OFTHE DISCLOSURE BACKGROUND OF THE INVENTION Field of the invention Thisinvention relates to a multi-layer color photo graphic material, moreparticularly it relates to a multilayer color photographic film havingan improved spectral sensitivity distribution of the blue-sensitiveemulsion layer thereof. That is to say, the invention relatesparticularly to a color photographic film or a color paper suitable formaking color prints from a transparent positive or a color negativehaving insuflicient masking.

Description of the prior art Many methods have been known for makingcolor photographs, but the method most employed at present is asubtractive color process based on the three primary color theory.

Dyes composing the color photographic image in the subtractive colorprocess usually comprise a yellow dye having an absorption maximum at420-460 nm., a magenta dye having an absorption maximum at 520- 570 nm.,and a cyan dye having an absorption maximum at 640-700 nm. However, theshape of the spectral absorption curve of each of the dyes used inpractice is broad with respect to the wavelength, and each of the dyeshas an undesirable absorption at a region other than the necessaryabsorption region. This undesirable absorption by the dye is one of thefactors which induces a reduction in the color reproduction property ofcolor photographic images. Further, when such a color photographic imageis used for making color prints, the color reproduction property isfurther reduced.

In order to minimize the deteriorating influence of the undesirableabsorption in making color prints in such a case, one technique whereina light-sensitive material containing a masking mechanism therein isemployed in the ordinary negative to positive process. However, in thecase of making color prints from a transparent positive, such a maskingtechnique (incorporated mask) cannot be employed and it is necessary touse complicated procedures such as an additional masking film and anaddi-' tional masking step.

Therefore, if a color print is made using a transparent positive or acolor photographic image formed with inf suflicient masking, colormixing will occur to reduce the .color saturation.

In a green-sensitive emulsion layer and a red-sensitive emulsion layerof a general color photographic material for color prints, thespectrally sensitive region of each' of the emulsion layers is sharplyseparated by the use of a proper sensitizing dye and thereby thedesirable maximum wave-length region of the spectral sensitivity isdetermined.

However, in a blue-sensitive emulsion layer of an ordinary colorphotographic material having silver halide emulsion layers, theabsorption region intrinsic to the silver halide in the emulsion isutilized and thus the spectrally sensitive region of the blue-sensitivelayer is broad, a factor greatly different from the green-sensitivelayer and the red-sensitive layer which are each spectrally sensitizedwith a dye. In short, the reduction in the color reproduction propertyof the blue-sensitive layer caused by the undesirable absorption of thedye described above has heretofore been considered unavoidable.

SUMMARY OF THE INVENTION One object of this invention is to provide amulti-layer type color photographic light-sensitive materialillustrating lowered color mixing which also has a color reproductionalmost the same as the original.

A further object of this invention is to provide a multilayer typephotographic silver halide light-sensitive material for prints whereinthe spectrally sensitive maximum wavelength of the blue-sensitiveemulsion layer is a wavelength region which includes less undesirableside absorptions of the cyan dye and magenta dye and which is almost thesame as the absorption maximum of a yellow dye, that is to say, in theregion of substantially from 440 nm. to 460 nm.

Another object of this invention is to provide a process of producingsuch a multi-layer type color photographic light-sensitive material.

. These objects of the invention are attained by incorporating at leastone dye having an absorption maximum in the wavelength region shorterthan 440 nm. and/or a dye having an absorption maximum at 460-520 nm. inthe blue sensitive photographic emulsion layer and/ or in at least oneof the layers, which may be a silver halide emulsion layer, of amulti-layer type silver halide color photographic light-sensitivematerial for color prints, which is coated over the blue sensitivephotographic emulsion layer, whereby the spectrally sensitive wavelengthregion of the blue-sensitive layer is substantially limited to 440-460nm. region.

DETAILED DESCRIPTION OF THE INVENTION wherein R represents an aminogroup, a hydroxyl group, or -OR' (where R is a methyl group or an ethylgroup) and X, represents -COO"M+ or SO -M+ (M+ is a cation such as ahydrogen ion, an alkali metal ion such as a sodium ion or a potassiumion, or an ammonium ion, preferably M+ is a potassium ion).

Any combination of groups R and X may be used. By changing R, theposition (wavelength) of the absorption maximum may shift, but it is inthe range of from about 360 nm. to about 430 nm.

General Formula II:

N C-OH wherein R and X are the same as R and X.

Any combination of the groups of R and X can be used and the absorptionmaximum is at about 500 nm.

The amount of the dyes of the General Formula I, II, and III is notcritical and generally a range of these dyes in an amount of from about3 10- to about 3X10 mole/mole silver halide based on the silver halidepresent in the blue-sensitive silver halide emulsion layer can be used.

Practical examples of the dyes used in this invention and the synthesesthereof are illustrated below.

Dye 1:

oaNa

SYNTHESIS 1 A mixture of 17.3 g. (1/10 mole) of sulfanilic acid, 7.3 g.of sodium nitrite, 44 cc. of a aqueous sodium hydroxide solution, and 50cc. of water was prepared and was designated solution A. Ice was addedto an aqueous hydrochloric acid solution of 32 cc. of concentratedhydrochloric acid and 70 cc. of water and, under stirring, the mixtureunder the condition that the temperature of the mixture was not over 100., solution A prepared above was added dropwise to the mixture.

After the addition was completed, the mixture was further stirred for 30minutes at temperatures of lower than 10 C. to obtain an aqueoussolution of a diazo" compound.

pyrazolone was dissolved in a mixture of 100 cc. of 10% and, understirring, the aqueous diazo compound solution prepared above was addeddropwise to the solution thus prepared, whereby a coupling reactionoccurred to form a dye. 1000 cc. of aqueous saturated sodium chloridesolution was added to the solution of the dye to cause salting out. Thedye was recovered by filtration and then subjected to salting out againto obtain 25 g. of the desired product.

The aqueous solution of the dye has its desired absorption maximum at430 nm.

Dye 2:

II I LL s 03K 03K SYNTHESIS 2 13 g. of1-(p-sulfophenyl)-3-oxy-5-pyrazolone was dissolved in 200 cc. ofmethanol and 10 cc. of triethylamine with stirring, and after adding 5g. of diphenylformamidine to the solution the mixture was heated for 3hours on a water bath under refluxing.

On the other hand, 7 g. of anhydrous potassium acetate was dissolved in100 cc. of methanol with heating and the solution was added to thesolution prepared above, whereby the potassium salt of the desired dyewas precipitated. The system was cooled to room temperature, recoveredby filtration under suction, washed with methanol and dried to give 9 g.of the desired product.

The aqueous solution of the dye had its absorption maximum at 384 nm.

Dye 3:

SYNTHESIS 3 cedure of Synthesis 2.

' maximum at 396 nm.

SYNTHESIS 4 .11 g. of 3-amino-l-(p-carboxy)-5-pyrazolone was dissolvedin a mixture of 200 cc. of methanol and 15 cc. of triethylamine andafter adding 6.4 g. of malondialdehydedianil hydrochloride to thesolution, the mixture was heated for 3 hours on a water bath withrefluxing. 3.1 g. of potassium hydroxide was dissolved in cc. of meth--anol with heating, and after filtering the resulting solu- C=O HO- l503K 503K SYNTHESIS Dye 5 was obtained from pyrazolone andmalondialdehydedianil following the procedure of Synthesis 4. Theaqueous solution of the dye had its absorption maximum at 492 nm.

Dyes other than the above can be produced by methods similar to those ofSyntheses 1, 2 and 4.

By the present invention, color reproduction is markedly improved, inparticular the mixing of yellow dye into a cyan dye and a magenta dyewhen a cyan dye and a magenta dye of an original are printed, i.e., theoccurrence of undesirable coloring in the blue-sensitive emul sionlayer, is greatly reduced.

The color photographic light-sensitive materials of this invention havenever been known, and even if it would be anticipated that the colorreproduction might be improved if the region of sensitivity distributionwas narrowed, a method of accurately controlling the spectrallysensitive region as in the present invention has never been known.

The incorporation of the dye referred to above in a color photographicmaterial for prints means that a bluesensitive emulsion layer, agreen-sensitive emulsion layer, and a red-sensitive emulsion layer areinsensitive to light of the Wavelength region cut by the dye, and thusthe dye of this invention may be incorporated in the bluesensitivesilver halide photographic emulsion layer and/or in any emulsion layerof the light-sensitive material coated on the blue-sensitive silverhalide photographic emulsion layer. It is particularly preferable toincorporate the dye of this invention in the blue-sensitive emulsionlayer or in a protective gelatin layer coated on the bluesensitiveemulsion layer.

The dyes previously described may be added to the emulsion layer alone,but better results can be obtained when a combination of suitable dyesis added as shown in examples of this invention.

The incorporation of such a dye or dyes is accompanied by, as a matterof course, a reduction in sensitivity of the blue-sensitive emulsionlayer and in this case it is required to use a silver halide emulsionhaving a higher sensitivity, as compared with the case of using no suchdye. Accordingly, it is natural that the yellow dye image in theblue-sensitive layer becomes coarser, but because the granularity of theyellow dye image is not as important as the grain shape of the magentadye, the minor influence thereof may be ignored.

By the addition of the dye light scattering is also reduced, and inparticular the reproduction of the fine details of the image isimproved. This is quite desirable in printing materials.

Practical embodiments and the merits of our invention are explainedfurther in detail by the following examples. The dyes used in thisinvention are not limited to the dyes shown in the examples, but anydyes satisfying the conditions previously indicated can be used in thisinvention.

Example 1 A red-sensitive emulsion was prepared in the following manner.300 g. of a 5.2 wt. percent aqueous gelatin solution was added to 700 g.of a negative photographic emulsion consisting of 77 g. of silveriodo-bromide grains containing 3 mole percent iodide ions and having amean grain size of 0.35 micron, 49 g. of gelatin and 574 g. of water andthen the mixture was maintained at 35 .0 C. to yield a sol.

ml. of a methanol solution of a 0.05% of anhydro 9 ethyl 3,3 (2 hydroxy1-sulfoprop-yl)-naphthothiacarbocyanine hydroxide and then 40 ml. of a0.5% aqueous solution of S-methyl-7-hydroxy-1,3,4-triazaindrizine wereadded to the sol. One gram of a cyan coupler,N-n-dodecyl-1-hydroxy-2-naphthoic acid amide, was dissolved in a mixtureof 1 ml. of dibutyl phthalate and 2 ml. of ethyl acetate by heating andthe solution Was dispersed by emulsification in 10 g. of a 10 Wt.percent aqueous gelatin solution in the presence of 1.2 ml. of a 5%aqueous solution of sodium dodecylsulfate. The coupler dispersion thusprepared was added to the mixture prepared above so that the content ofthe coupler was 0.2 mole per mole of silver halide.

Furthermore, 10 ml. of a 2% aqueous solution of l-hydroXy-3,5-dichloro-S-triazine sodium salt and 2 ml. of a 4% aqueous solution ofsaponin were added to the mixture.

The silver halide emulsion for the red-sensitive emulsion layer thusprepared was coated on a cellulose triacetate support (so that the drythickness of the layer was 4.0/1.) having an antihalation layer, andthen a thin gelatin layer was coated on the red-sensitive emulsionlayer.

A green-sensitive emulsion was prepared in the following manner. 300 g.of a 5.2 wt. percent aqueous gelatin solution was added to 700 g. of anegative photographic emulsion consisting of 77 g. of silveriodo-bromide grains containing 3 mol percent iodide ions and having ameans grain size of 0.43 micron, 49 g. of gelatin and 574 g. of water,and the mixture was maintained at 35.0 C. to yield a so 110 ml. of a0.1% methanol solution of anhydro-3,3'-disulfopropyl-9-ethyl-5,5'-diphenyl oxacarbocyanine hydroxide and then40 ml. of a 0.5 aqueous solution of 5-methyl-7-hydroxy-1,3,4-triazaindrizine were added to the sol. 1.5 of amagenta coupler, 1-(2,4,6-trichlorophenyl)- 3-dodecylamido-S-pyrazolonewas dissolved in a mixture of 1.5 ml. of tricresyl phosphate and 2 ml.of ethyl acetate under heating, and the solution was dispersed, byemulsification in 10 g. of a 10 wt. percent gelatin solution in thepresence of 1.2 ml. of a 5% aqueous solution of sodrum dodecylsulfate.The coupler dispersion thus prepared was added to the silverhalide-containing mixture prepared above so that the content of thecoupler was 0.23 mole per mole of silver halide. Moreover, the samehardening agent and surface active agent as in the case of preparing thered-sensitive emulsion layer were added to the photographic emulsion forgreen-sensitive emulsion layer.

The photographic emulsion for the green-sensitive emul- S1011 layer thusprepared was coated on the thin gelatin layer on the red-sensitiveemulsion layer formed above so that the dry thickness of the layer was4.5 microns. Onto the green-sensitive emulsion layer a yellow colloidalsilver gelatin layer containing colloidal silver of a 0.03 micron meangrain size was uniformly coated to a dry thickness of 1.0 micron.

Then, the following two kinds of emulsion for the bluesensitive emulsionlayer were prepared, and each of them was coated onto samples of thecolloidal silver-containing gelatin layer on the green-sensitiveemulsion layer. These light-sensitive films were named Specimen 1 andSpecimen 2, respectively.

Specimen 1.- g. of a 5.2% aqueous gelatin solution was added to 850 g.of the same silver halide emulsion (the mean grain size of the silverhalide was 0.43

micron) used in preparing the green-sensitive emulsion layer, and themixture was maintained at 35 C. to yield a sol. The following materialswere added successively to the sol.

40 ml. of a 0.5% aqueous solution of-methyl-7-hydroxy-1,3,4-triazaindrizine was added to the sol; 1.5 g of ayellow coupler, 4-dodecylbenzoyl-2-methoxy-acetan1l1de was dissolved ina mixture of 2.0 ml. of dibutyl phthalate and 1.5 ml. of ethyl acetateunder heating and the solution obtained was dispersed by emulsificationin g. of a 10 wt. percent aqueous gelatin solution in the presence of1.2 ml. of 5% aqueous solution of sodium dodecylsulfate. The couplerdispersion obtained was added to the silver halide emulsion mixtureprepared above so that the content of the coupler was 0.22 mole per moleof silver halide. Moreover, the same hardening agent and surface activeagent as used in producing the green sensitive emulsion layer were addedto the blue-sensitive photographic emulsion.

The blue-sensitive emulsion thus prepared was coated onto the yellowcolloidal silver-gelatin layer formed on the green-sensitive emulsionlayer (as indicated above) to a dry thickness of 5 microns, and then athin gelatin layer was coated onto the blue-sensitive layer as aprotective layer to give Specimen 1.

Specimen 2.l50 g. of 5.2 wt. percent aqueous gelat n solution was addedto 850 g. of a negative photographic emulsion consisting of 93 g. ofsilver halide grains containing 3 mole percent iodide ions and having amean grain size of 0.6 micron, 60 g. of gelatin, and 697 g. of water,and the mixture was maintained at 35 C. to yield a sol. Then, 100 ml. ofa 5% aqueous solution of 4,4-bis[3- amino 1(p-sulfo-phenyl)-pyrazole-5-on]-monomethineoxonol dipotassium salt(absorption maximum wave length 396 nm.) was added to the sol preparedabove. The stabilizer, yellow coupler emulsion, hardening agent, andsurface active agent added were the same as in preparing Specimen 1 toproduce the blue-sensitive emulsion for Specimen 2. The blue-sensitiveemulsion thus prepared was coated onto the yellow colloidalsilver-gelatin layer on the green-sensitive emulsion layer formed aboveto a dry thickness of 5 microns, and then a thin gelatin layer wascoated uniformly onto the blue-sensitive layer as a protective layer toyield Specimen 2.

By subjecting each of the two specimens, Specimen 1 and Specimen 2 to areversal processing by an ordinary developing solution, a positive colorimage was obtained in each case. The compositions of the developingsolution were as follows:

Black and white developing solution Water ml.. 800N-methyl-p-aminophenol g 4.5 Hydroquinone g 5.5 Anhydrous sodium sulfiteg 50 Sodium carbonate (mono-hydrate) g 30.5 Potassium bromide g 1.5 0.1%aqueous potassium iodide solution ml 10 Potassium thiocyanide (10%aqueous soln.) ml 20 Water added to make the total volume 1 liter.

Color developing liquid Water ml 800 Benzyl alcohol ml 5.0 Anhydroussodium sulfite g 5.0 Tri'sodium phosphate (12-H O) g 40 Sodium hydroxideg 1.5 Potassium bromide g 0.5 Ethylene diamine ml 5.0 Citrazinic acid g1.5 p amino N ethyl N B methanesulfonamidoethyl-m-toluidine sulfate g10.5

Water added to make the total volume 1 liter,

The reversal processing for the specimens was conducted in the followingmanner.

The specimen was developed by the black and white developing solutionhaving the above composition for 10 minutes at 24 C., then washed withwater, and the whole area of the specimen was exposed uniformly tointense white light. Then, the specimen was developed by the colordeveloping solution having the above-mentioned composition for 15minutes at 24 C., washed with water, bleached, fixed, and washed withwater.

In addition to these specimens, a light-sensitive film having only ared-sensitive emulsion layer containing the cyan coupler as describedhereinbefore in Example 1 was prepared, exposed to a tungsten lamp of acolor temperature of 2854 K. through a conventional optical wedge, andsubjected to the above-mentioned reversal processing using thedeveloping solution indicated above, whereby a cyan colored strip, wasobtained. I

Each of Specimen 1 and Specimen 2 was exposed to a tungsten lamp of acolor temperature of 2854 K. using the cyan-colored strip obtained aboveinstead of the optical wedge to obtain a print image.

The color mixing of the print was evaluated by comparing the gradientratio of the R density and the G density 'y /y and also the gradientratio of the R density and the B density /7 of the specimens with thoseof the cyan colored strip which is designated the original. The resultsare shown in Table 1.

The specimen identified as Specimen 1 in Example 1 was prepared asSpecimen 1 of this example.

Specimen 3 was prepared by coating a blue-sensitive emulsion prepared asbelow onto the yellow colloidal layer on the same green-sensitiveemulsion layer as in Specimen 1, Le, both specimens were identicalexcept for the blue-sensitive emulsion.

That is to say, 150 g. of a 5.2 wt. percent aqueous gelat1n solution wasadded to 850 g. of a negative photographic emuls on-consisting of 93 g.of silver iodo-bromide grains contain ng 3 mole percent iodide ions andhaving a mean grain size of 0.8 micron, 60 g. of gelatin, and 697 g. ofwater, and the mixture was maintained at 35 C. to yield a so ml. of a 5%aqueous solution of 4,4-bis[3-amino- 1 (p sulfophenyl) pyrazole 5 on]-monomethineoxonole dipotassium salt and 30 ml. of a 10% aqueoussolution of 4 (p sulfophenylazo) 3 carboxy-l-(psulfophenyDpyrazole 5 ontrisodium salt (absorption maximum wavelength: 430 mm.) were added tothe sol and further the samestabilizer, yellow coupler emulsion,hardening agent, and surface active agent as used in formmg Specimen 1were added thereto to give the emulsion for .the blue-sensitive layer.This blue-sensitive emulsion was coated onto the yellow colloidalsilver-gelatin layer on the green-sensitive emulsion layer which wasfurther formed on the red-sensitive emulsion layer of the same structureas in Specimen 1 to a dry thickness of 5 microns.

A thin gelatin layer was uniformly coated onto the bluesensitive layeras a protective layer to give Specimen 3.

Onto each of the specimens, Specimen 1 and Specimencolored strip wasprinted, and the specimens were subjected to the same developingprocedures as in Example 1. The results are shown in Table 2 and Table3.

EXAMPLE 3 Specimen 1 in this example was the same as Specimen l inExample 3. Specimen 4 was prepared by coating the photographic emulsionfor the blue-sensitive emulsion layer prepared as below onto thegreen-sensitive emulsion layer having the same composition as Specimen1.

That is to say, 150 g. of a 5.2 wt. percent aqueous gelatin solution wasadded to 850 g. of a negative photographic emulsion consisting of 93 g.of silver iodo-bromide grains containing 3 mole percent iodide ions, 60g. of gelatin, and 697 g. of water, and the mixture was maintained at 35C. to yield a sol.

100 ml. of a 5% aqueous solution of 4,4-bis[3-amino-l-(p-sulfophenyl)pyrazole 5 on]-monomethineoxonole dipotassium salt, 30ml. of a aqueous solution of 4- (p sulfophenylazo) 3 carboxy 1 (psulfophenyl)- pyrazole 5 on trisodium salt, and then 30 ml. of 5%aqueous solution of 4,4 bis[3 oxy 1 (p sulfophenyl)pyrazole 5 one]trimethineoxonol dipotassium salt (absorption maximum wavelength: 492nm.) were added to the sol, and the same stabilizer yellow coupleremulsion, hardening agent, and surface active agent as in Specimen lwere further added to the above mixture. The blue-sensitive emulsionthus prepared was coated onto the colloidal silver-gelatin layer on thegreen-sensitive emulsion layer further formed on the red-sensitiveemulsion layer the same as in Specimen 1 to a dry thickness of 5 micronsto give Specimen 4.

Onto each of Specimen 1 and Specimen 4 the cyancolored strip prepared asin Example 2 (or the magentacolored strip prepared as in Example 2) wasprinted, and each of them was subjected to the same developingprocedures as in Example 2. The results are shown in Table 4 and Table5.

(Original was magenta-colored specimen) 'YB/'YG Original 0.30 Specimen 10.45 Specimen 4 0.33

As is clear from Examples l-3 and the results shown in Tables l-S, theratios 'y /q and 'y l'y of the lightsensitive materials of thisinvention are far nearer the values of the originals as compared withthe light-sensitive materials containing no dyes of this invention. Inother words, by limiting the maximum distribution of the spectralsensitivity of the blue-sensitive emulsion layer to substantially440-460 nm. by incorporating the dye of this invention, yellow dyemixing in the case of printing an image composed of a cyan dye and amagenta dye as an original can be remarkably reduced and a color printhaving color tones substantially the same as that of the original can beobtained.

While the invention has been particularly shown and described withreference to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the spirit and scope of theinvention.

What we claim is:

1. A multiple layer type color photographic silver halidelight-sensitive material for color prints having at least ablue-sensitive photographic emulsion layer in which the spectralsensitivity of the blue-sensitive silver halide emulsion layer islimited to the region of about 440 to about 460 nm. wherein at least onedye having its absorption maximum at a wave length region shorter thanabout 440 nm. and/or in a region of about 460 to about 520 nm. isincorporated in said blue-sensitive photographic layer and/ or in atleast one layer coated on said blue-sensitive photographic emulsionlayer of the lightsensitive material.

2. The material of claim 1 wherein the dye is of the formula:

it 5:0 HO-ii It wherein R represents an amino group, a hydroxyl group,or OR', wherein R is a methyl group or an ethyl group and X representsCOOM or SO M+, wherein M+ is a cation.

3. The material of claim 1 wherein the dye is of the formula:

wherein R represents a methyl group, COOC H or -COO-M X and Y eachrepresents a hydrogen atom or -SO M+, wherein M+ and M each is a cation.

4. The material of claim 1 wherein the dye is of the formula:

1 1 wherein R represents an amino group, a hydroxyl group, or -OR',wherein R is a methyl group or an ethyl group and X represents COO-M+ or--SO M wherein M+ is a cation.

5. The material of claim 2 wherein said dye is present in said elementat a level of from about 3 10 to 3x10- mole/mole of silver halide insaid blue-sensitive photographic emulsion layer.

6. The material of claim 3 wherein said dye is present in said elementat a level of from about 3X 10" to 3X 10- mole/mole of silver halide insaid blue-sensitive photographic emulsion layer. V

7. The material of claim 4 wherein said dye is present in said elementat a level of from about 3 1 0 to 3X l0 mole/mole of silver halide insaid blue-sensitive photographic emulsion layer.

8. The material of claim 2 wherein M+ is selected from the groupconsisting of a hydrogen ion, an alkali metal ion and an ammonium ion.

9. The material of claim 8 wherein M is a potassium 10D.

10. The material of claim 3 wherein M is a sodium ion or a potassiumion.

11. The material of claim 4 wherein M is selected from the groupconsisting of a hydrogen ion,an alkali metal ion and an ammonium ion. i

12. The material of claim 11 wherein M+ is a potassium ion.

13. The material of claim 1 wherein said dye is incorporated in saidblue-sensitive photographic emulsion layer and/or a gelatin protectivelayer coated on, said blue- 7 sensitive photographic emulsion layer.

NORMAN G. TORCHIN, mini Examiner A. T. SURO PICO, Assistant Examiner US.Cl. X.R.

